WO2000058425A1 - Composition d'huile pour machine de refrigeration - Google Patents

Composition d'huile pour machine de refrigeration Download PDF

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Publication number
WO2000058425A1
WO2000058425A1 PCT/JP1999/004496 JP9904496W WO0058425A1 WO 2000058425 A1 WO2000058425 A1 WO 2000058425A1 JP 9904496 W JP9904496 W JP 9904496W WO 0058425 A1 WO0058425 A1 WO 0058425A1
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change
group
oil composition
acid
ester
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PCT/JP1999/004496
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English (en)
Japanese (ja)
Inventor
Yuji Shimomura
Satoshi Suda
Hiroyuki Hirano
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Nippon Mitsubishi Oil Corporation
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Priority to AU53030/99A priority Critical patent/AU5303099A/en
Publication of WO2000058425A1 publication Critical patent/WO2000058425A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/38—Conveyors or chain belts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/44—Super vacuum or supercritical use
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/50—Medical uses

Definitions

  • the present invention relates to a refrigerator oil composition, and more particularly to a refrigerator oil composition containing an alicyclic dicarboxylic acid ester compound.
  • HFC refrigerants can also be subject to regulation from the perspective of global warming, and the use of natural refrigerants such as carbon dioxide, ammonia, and hydrodynamic hydrogen is being considered.
  • Refrigeration oil requires many performances such as lubricity, refrigerant compatibility, heat and hydrolysis stability, electrical insulation, and low moisture absorption.
  • a compound is selected.
  • refrigeration oils for HFCs include oxygen-containing compounds such as esters, ethers, and carbonates that are compatible with refrigerants, or alkylbenzenes that have poor refrigerant compatibility but have excellent lubricity and thermal and hydrolytic stability. Etc. are used.
  • An ester-based refrigerating machine oil is obtained by reacting an aliphatic polyhydric alcohol with a fatty acid as disclosed in Japanese Patent Application Laid-Open Publication No. Hei 3 (1993) -502602. Polyol esters are known, and such ester-based refrigerating machine oils have a low viscosity.
  • One of the effective measures is to select a fatty acid having a small carbon number in the alkyl group of the fatty acid used as a raw material.
  • the alkyl group of the fatty acid becomes small, a problem occurs in that the heat and hydrolysis stability of the obtained ester is reduced.
  • Japanese Patent Application Laid-Open No. 9-122211 is an ester refrigerating machine oil with excellent heat and hydrolysis stability.
  • the present invention has been made in view of the above-mentioned problems of the related art, and when used together with HFC refrigerant and natural refrigerants such as carbon dioxide and hydrodynamic carbon, lubricity, refrigerant compatibility, heat ⁇ It is an object of the present invention to provide a refrigerating machine oil composition which is excellent in hydrolytic stability, electric insulation properties, etc. and enables high efficiency of a refrigerating system.
  • HFC refrigerant and natural refrigerants such as carbon dioxide and hydrodynamic carbon, lubricity, refrigerant compatibility, heat ⁇
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a refrigerating machine oil composition excellent in various performances can be obtained by using a base oil containing a specific ester oil. .
  • the refrigerator oil composition of the present invention has an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are adjacent to each other on the alicyclic ring.
  • a cis-type alicyclic dicarboxylic acid ester compound which is bonded to a carbon atom and is cis-form with respect to two orientations of the ester group
  • R 1 represents a hydrocarbon group having 0 to 3 carbon atoms, R 1 for each ester group They may be the same or different.
  • the refrigerator oil composition of the present invention preferably further contains an epoxy compound and / or a phosphorus compound.
  • an epoxy compound at least one compound selected from the group consisting of a phenylglycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound and an epoxidized fatty acid monoester is preferable. Type epoxy compounds and / or alicyclic epoxy compounds are more preferred.
  • a fluid composition for a refrigerator according to the present invention contains the refrigerator oil composition of the present invention and a non-chlorine-containing chlorofluorocarbon.
  • the cis-type alicyclic dicarboxylic acid ester compound according to the present invention refers to an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are alicyclic rings. It bonds to adjacent carbon atoms on the formula ring and is cis-form with respect to the two orientations of the ester group.
  • R 1 represents a hydrocarbon group having 0 to 3 carbon atoms, R 1 for each ester group may be the same or different.
  • the alicyclic ring referred to here includes a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, and the like, and a cyclohexane ring and a cyclohexene ring are preferable. .
  • a cyclohexane ring is more preferable because of a small increase in viscosity when used under long-term or severe conditions, and a cyclohexene ring is preferably used when a long-term or severe condition is used.
  • the cis-type alicyclic dicarboxylic acid ester compound needs to have two alicyclic rings and two ester groups represented by the above formula (1). It is not preferred that the number of ester groups is one, because the compatibility with the refrigerant and the stability of heat and hydrolysis are insufficient. When the number of ester groups is 3 or more, it is not preferable from the viewpoint of low-temperature fluidity.
  • the two ester groups represented by the above formula (1) are bonded to mutually adjacent carbon atoms on the alicyclic ring from the viewpoint of thermal and hydrolytic stability, and furthermore, the two ester groups It is necessary to be a cis-body with respect to the orientation of.
  • R 1 in the above formula (1) represents a hydrocarbon group having 1 to 30 carbon atoms, preferably 2 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms.
  • the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group.
  • an alkyl group, a cycloalkyl group or an alkylcycloalkyl group is preferred from the viewpoint of stability of hydrothermal decomposition.
  • the alkyl group may be linear or branched.
  • Examples of the alkyl group having 3 to 18 carbon atoms include, for example, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group , Linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear Or a branched decyl group, a linear or branched pendecyl group, a linear or branched dodecyl group, a linear or branched tridecyl group, a linear or branched Tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched hepdecyl decyl group, linear or branched And a decyl group.
  • the linear alkyl group is preferably a group having 5 or more carbon atoms from the viewpoint of thermal and hydrolytic stability, and is preferably a group having 18 carbon atoms or less from the viewpoint of refrigerant compatibility.
  • the branched alkyl group preferably has 3 or more carbon atoms from the viewpoint of heat and hydrolysis stability, and has 18 or less carbon atoms from the viewpoint of refrigerant compatibility.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, and a cyclohexyl group is preferred from the viewpoint of heat and hydrolysis stability.
  • the alkylcycloalkyl group is a group in which an alkyl group is bonded to a cycloalkyl group, and is preferably a group in which an alkyl group is bonded to a cyclohexyl group from the viewpoint of heat and hydrolysis stability.
  • the alkylcycloalkyl group preferably has a total carbon number of 6 or more from the viewpoint of heat and hydrolysis stability, and preferably has a total carbon number of 10 or less from the viewpoint of refrigerant compatibility and low-temperature fluidity. .
  • the cis-type alicyclic dicarboxylic acid ester compound one or more hydrocarbon groups may be bonded to a carbon atom on the alicyclic ring.
  • a hydrocarbon group an alkyl group is preferable, and a methyl group is particularly preferable.
  • the cis-type alicyclic dicarboxylic acid ester compound referred to in the present invention has the above-mentioned structure.
  • Such an ester compound is prepared by converting a predetermined acid component and an alcohol component according to a conventional method, preferably using nitrogen or the like. It is prepared by esterification while heating under an inert gas atmosphere, under an atmosphere of an esterification catalyst or under no catalyst.
  • the acid component of the cis-type alicyclic dicarboxylic acid ester compound is cis-cycloalkanedicarboxylic acid, cis-cycloalkenedicarboxylic acid or an acid anhydride thereof, and two ester groups are formed on the alicyclic ring. And those bonded to carbon atoms adjacent to each other, and these can be used as one kind or as a mixture of two or more kinds.
  • Carboxylic acid, cis-4-methyl-1-, 2-cyclohexanedicarboxylic acid, cis-3-methyl-4-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-4-cyclohexene-1 , 2-Dicarboxylic acids and their anhydrides are disclosed.
  • cis-1,2-cyclohexanedicarboxylic acid, cis-3-methyl-1,1,1-methyl-1,1,2-cyclohexyldicarboxylic acid are used from the viewpoint of suppressing the increase in viscosity of the prepared ester compound when used under long-term or severe conditions.
  • 2-cyclohexanedicarboxylic acid, cis-4-methyl-1,2-cyclohexanedicarboxylic acid and their acid anhydrides are preferred, while increasing the total acid value when used under long-term or severe conditions.
  • cis-4-cyclohexene-1,2-dicarboxylic acid cis-1-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-11,2-cyclohexanedicarboxylic acid
  • Preferred are cis-3-methyl-4-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-14-cyclohexene-1,2-dicarboxylic acid and their anhydrides.
  • cis_4-cyclohexene-1,2-dicarboxylic acid can be obtained by reacting butadiene and maleic anhydride at 100 ° C. in a benzene solvent.
  • the alcohol component of the cis-type alicyclic dicarboxylic acid ester compound includes a linear alcohol having 3 to 18 carbon atoms, a branched alcohol having 3 to 18 carbon atoms, and a cycloalcohol having 5 to 10 carbon atoms. Is mentioned. Specific examples include linear or branched propanol (including n-propanol and 1-methylethanol), and linear or branched butanol (n-butanol and 1-methylpropanol).
  • Linear or branched decanol including n-decanol, iso-decanol, etc.
  • linear or branched decanol including n-decanol, etc.
  • Linear Or branched dodecanol including n-dodecanol, iso-dodecanol, etc.
  • linear or branched tridecanol linear or branched tetradecanol (n-tetradecanol) Octanol, iso-tetradecanol, etc.
  • linear or branched pentadecanol linear or branched hexadecanol, n-hexanol, iso-hexade
  • Linear or branched heptane decanol linear or branched octadecanol (n- or octadecanol, etc.) Hex), methylhexanol, methylcyclohexanol,
  • the alcohol component is used, for example, in an amount of 1.0 to 1.5 equivalents, preferably 1,05 to L.2 equivalents, per equivalent of the acid.
  • a lower alcohol ester of the acid component and / or an acetic acid ester or a propionic acid ester of the alcohol are used, and a cis-type aliphatic dicarboxylic acid ester compound is subjected to a transesterification reaction. It is also possible to get
  • esterification catalyst examples include Lewis acids, alkali metal salts, and sulfonic acids.
  • Specific examples of the Lewis acid include aluminum derivatives, tin derivatives, and titanium derivatives.
  • Examples of the alkali metal salts include sodium alkoxide and potassium alkoxide, and examples of the sulfonic acids include paratoluenesulfonic acid, methanesulfonic acid, and sulfuric acid.
  • the amount used is, for example, about 0.1 to 1% by mass based on the total amount of the raw material acid component and alcohol component.
  • the temperature for esterification is, for example, 150 ° C. to 230 ° C., and the reaction is usually completed in 3 to 30 hours.
  • the ester compound is purified by a conventional purification method, for example, adsorption purification treatment such as liquid-liquid extraction, reduced pressure distillation, and activated carbon treatment. can do.
  • adsorption purification treatment such as liquid-liquid extraction, reduced pressure distillation, and activated carbon treatment.
  • the content of the cis-type alicyclic dicarboxylic acid ester compound in the refrigerator oil composition of the present invention is not particularly limited, the excellent various performances of the cis-type alicyclic dicarboxylic acid ester compound can be further derived. It is preferably contained in an amount of at least 5% by mass, more preferably at least 10% by mass, even more preferably at least 30% by mass, more preferably at least 50% by mass, based on the total amount of the refrigerator oil composition. Is most preferred.
  • the cis-type alicyclic dicarboxylic acid ester compound is mainly used as a base oil.
  • the base oil of the refrigerator oil composition of the present invention only the cis-type alicyclic dicarboxylic acid ester compound may be used, but in addition to the cis-type alicyclic dicarboxylic acid ester compound specified in the present invention such as a polyol ester or a complex ester.
  • Synthetic oils containing oxygen such as esters other than cyclic dicarboxylic acid ester compounds, polyglycols, polyvinyl ethers, ketones, polyphenylene ethers, silicones, polysiloxanes, and perfluoroethers may be used in combination. .
  • the amount of the synthetic oil containing oxygen is not particularly limited. However, from the viewpoint of improving the thermal efficiency and the stability of heat and hydrolysis of the refrigerating machine oil, 100 parts by weight of the cis-type alicyclic dicarboxylic acid ester compound is The amount of the synthetic oil containing oxygen is preferably at most 150 parts by weight, more preferably at most 100 parts by weight.
  • the refrigerating machine oil composition of the present invention contains a cis-type alicyclic dicarboxylic acid ester compound and, if necessary, a synthetic oil containing oxygen, and is mainly used as a base oil.
  • the refrigerating machine oil composition of the present invention can be suitably used in a state in which no additives are added, but may be used in a form in which various additives are blended as necessary.
  • a phosphate ester an acid phosphate, an amine salt of an acid phosphate, a chlorinated phosphate and a phosphite are used.
  • phosphate esters include triptyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, and tridecyl phosphate.
  • Tridecyl phosphate Tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripene decyl phosphate, trihexadecyl phosphate, trihepdecyl decyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate , Tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate and the like.
  • Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, and monodecyl.
  • Acid phosphate monoundecyl acid phosphate, mono Dodecyl acid phosphate, mono tridecyl acid phosphate, monotetradecyl acid phosphate, monopen decyl acid phosphate, monohexadecyl acid phosphate, monohepcyl decyl acid phosphate, monooctyl decyl acid phosphate Phosphate, mono-oleic acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate Didecyl acid phosphate, didecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipen Decyl acid phosphate Hue Ichito, hexadecyl acid phosphat
  • Examples of the amine salt of the acidic phosphoric acid ester include the acidic phosphoric acid ester methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine. And diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, and trioctylamine.
  • chlorinated phosphates include tris-dichloro propyl phosphate, tris-chloroethyl phosphate, tris-chloro phenyl phosphate, polyoxyalkylene bis [di (chloroalkyl). ] Phosphates and the like.
  • phosphites include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, octyl phosphite, dinonyl phosphite, didecyl phosphite, and didecyl phosphite.
  • the amount of the phosphorus compound is not particularly limited. However, the content is usually based on the total amount of the refrigerator oil composition (based on the total weight of the base oil and all the blended additives). It is desirable to add a phosphorus compound in such an amount that the amount becomes 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass.
  • At least one epoxy compound selected from the group consisting of:
  • phenylglycidyl ether type epoxy compound examples include phenylglycidyl ether and alkylphenylglycidyl ether.
  • the alkylphenyl glycidyl ether referred to herein includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, among which those having 1 alkyl group having 4 to 10 carbon atoms, for example, n-butylphenylglycidyl ether, i-butyl R-phenylglycidyl ether, S-C-butylphenylglycidyl ether, tert-butylphenylglycidylether, pentylphenylglycidylether, hexylphenyldaricidylether, heptylphenylglycidylether, octylphenylglycidylether Monoter, nonylphenylglycidylether, dec
  • alkylglycidyl ether type epoxy compound examples include decyl glycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, Ethyl hexyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, erythritol pentayl glycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether And polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether and the like.
  • glycidyl ester type epoxy compound examples include compounds represented by the following general formula (2).
  • R represents a hydrocarbon group having 1 to 18 carbon atoms.
  • R represents a hydrocarbon group having 1 to 18 carbon atoms.
  • a hydrocarbon group examples include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a carbon atom.
  • an alkyl group having 5 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a phenyl group and an alkyl group having an alkyl group having 1 to 4 carbon atoms are preferable.
  • glycidyl ester type epoxy compounds preferred are, for example, glycidyl-1,2,2-dimethyloctanoate, glycidylbenzoate, glycidyl-tert-butylbenzoate, glycidylacrylate, glycidylmethacrylate An evening create can be exemplified.
  • aryloxysilane compounds include 1,2-epoxystyrene
  • alkyloxysilane compound specifically, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxy Octane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxydedecane, 1,2-epoxidededecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,, Examples thereof include 2-epoxy pen decane, 1,2-epoxyhexadecane, 1,2-epoxyhepcane decane, 1,1,2-epoxy octane decane, 2-epoxynonadecane, and 1,2-epoxy icosane.
  • Examples of the alicyclic epoxy compound include compounds in which carbon atoms constituting an epoxy group directly constitute an alicyclic ring, such as a compound represented by the following general formula (3).
  • alicyclic epoxy compound examples include, for example, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-1,3,4-epoxycyclohexanecarboxy.
  • epoxidized fatty acid monoester examples include esters of epoxidized fatty acids having 12 to 20 carbon atoms and alcohols or phenols having 1 to 8 carbon atoms, and alkylphenols. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used.
  • epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
  • epoxy compounds a phenylglycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound, and an epoxidized fatty acid monoester are preferable because the thermal / hydrolytic stability can be further improved. And glycidyl ester type epoxy compounds and alicyclic epoxy compounds are more preferable.
  • the blending amount is not particularly limited, but usually the content is based on the total amount of the refrigerator oil composition (based on the total amount of the base oil and all the blended additives). It is desirable to mix the epoxy compound in such an amount that the amount becomes 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass.
  • a conventionally known refrigerating machine oil additive for example, a phenolic compound such as di-tert-butyl-p-cresol, bisphenol A, etc.
  • Antioxidants phenyl mono-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, etc., antioxidants based on amines, antiwear agents such as zinc dithiophosphate, chlorinated paraffin, sulfur Additives such as extreme pressure agents such as compounds, oil agents such as fatty acids, antifoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, cleaning dispersants, etc. Alternatively, it is also possible to mix several types.
  • the total blended amount of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less based on the total amount of the refrigerating machine oil composition (based on the total amount of the base oil and all the blended additives). is there.
  • the kinematic viscosity of the refrigerator oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to L 00 mm 2 / s, more preferably 4 to 50 mm 2 / s, and most preferably 5 to 50 mm 2 / s. 4040 mm 2 / s. Further, the kinematic viscosity at 100 ° C preferably 1 to 20 mm 2 / s, more preferably, to 2 to 10 mm 2 / s.
  • a feature of the refrigerating machine oil of the present invention that the heat and hydrolysis stability is good even when the viscosity is reduced is that the kinematic viscosity at 40 ° C is preferably 5 to 35 mm 2 / s, more preferably 5 to 25 mm 2 / s. 2 Zs, even more preferably between 5 and 20 mm 2 / s, most preferably between 5 and 15 mm 2 / s.
  • the volume resistivity of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably not less than 1.0 ⁇ , more preferably not less than 1.0 ⁇ 10 12 ⁇ ⁇ m, and most preferably not less than 1.0 ⁇ 10 12 ⁇ ⁇ ⁇ m. Preferably, it can be 1.0 ⁇ 10 13 ⁇ ⁇ cm or more. In particular, when used for hermetic refrigerators, high electrical insulation tends to be required.
  • the volume resistivity means a value at 25 ° C. measured in accordance with JISC2101 “Electric insulating oil test method”.
  • the water content of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerator oil composition. be able to. In particular, when used for hermetic refrigerators, it is required that the water content be low from the viewpoint of the thermal and hydrolytic stability of the oil and the effect on the electrical insulation.
  • the total acid value of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 0.1 mgCOH / g or less, more preferably, in order to prevent corrosion of metal used in the refrigerator or piping. 0.05 mgKOH / g or less.
  • the total acid value refers to the value of the total acid value measured in accordance with JIS K 2501 “Testing Method for Neutralization Value of Petroleum Products and Lubricating Oils”.
  • the ash content of the refrigerating machine oil composition of the present invention is not particularly limited. However, in order to enhance the thermal and hydrolytic stability of the refrigerating machine oil composition of the present invention and suppress the generation of sludge, it is preferably 100 ppm. Or less, more preferably 50 ppm or less.
  • the ash refers to the value of ash measured in accordance with JIS K 2272 "Test method for ash and sulfated ash of crude oil and petroleum products".
  • Refrigerants used in refrigerators using the refrigerator composition of the present invention include HFC refrigerants, fluorinated ether-based refrigerants such as monofluoroethers, non-fluorine-containing ether-based refrigerants such as dimethyl ether, and carbon dioxide and the like. These are natural refrigerants such as hydrocarbons, and these may be used alone or as a mixture of two or more.
  • HFC refrigerant examples include hydrofluorcarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms.
  • hydrofluorcarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms.
  • difluoromethane HFC-32
  • trifluoromethane HFC-23
  • pendufluorene HFC-125
  • 1,1,2,2-tetrafluoroethane HF C-134
  • 1, 1, 1, 1, 2—tetrafluorene HFC-134a
  • 1,1,1-trifluorene HFC—143a
  • 1,1-difluorene HFC—152a
  • These refrigerants are appropriately selected according to the required performance for the application.
  • examples of natural refrigerants include carbon dioxide and hydrocarbons.
  • a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant.
  • it is an alkane, cycloalkane, alkane or a mixture thereof having 1 to 5, preferably 1 to 4 carbon atoms.
  • methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, Methylcyclopropane or a mixture of two or more thereof is mentioned.
  • propane, butane, isobutane or a mixture thereof is preferred.
  • the refrigerating machine oil composition according to the present invention is usually present in a refrigerating machine in the form of a refrigerating machine fluid composition mixed with the above-described refrigerant.
  • the mixing ratio of the refrigerating machine oil composition and the refrigerant in the fluid composition is not particularly limited, but the refrigerating machine oil composition is preferably 1 to 500 parts by weight, more preferably 100 to 100 parts by weight of the refrigerant. It is 2 to 400 parts by weight.
  • the refrigerating machine oil composition of the present invention can be used as a lubricating oil for a refrigerant compressor of any refrigerating machine due to its excellent electrical properties and low moisture absorption.
  • Refrigerators used are, specifically, room air conditioners, package air conditioners, refrigerators, automotive air conditioners, dehumidifiers, freezers, freezer and refrigerated warehouses, vending machines, showcases, cooling equipment for chemical plants, etc. Is mentioned.
  • the refrigerator oil composition of the present invention is particularly preferably used for a refrigerator having a hermetic compressor.
  • the refrigerating machine oil composition of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, and a centrifugal type.
  • Tables 1 to 12 show the properties (kinematic viscosity at 40 ° C and 100 ° C and total acid value) of each of the obtained sample oils.
  • Base oil 1 diisoheptyl cis-1,2-cyclohexanedicarboxylate
  • Base oil 2 di (2-ethylhexyl) cis-1,2-cyclohexanedicarboxylate
  • Base oil 3 di (3,5,5-trimethylhexyl) cis-1,2-cyclohexanedicarboxylate
  • Base oil 4 cis-1,2-cyclohexanedicarboxylic acid di (2,6-14-1heptyl)
  • Base oil 5 diisodecyl cis-1,2-cyclohexanedicarboxylate
  • Base oil 6 cis-4-cyclohexene-1,2,2-diisoheptyl dicarboxylate
  • Base oil 7 cis-4-cyclohexene-1,1,2 di (2-ethylhexyl) dicarboxylate
  • Base oil 8 cis-4-cyclohexene-1-dicarboxylic acid di (3,5,5-trimethylhexyl)
  • Base oil 10 diisoheptyl cis-1,3-cyclohexanedicarboxylate
  • Base oil 12 penyu Erythritol and n-pentanoic acid, n-heptanoic acid and 3,
  • Example 1 Example 2 Example 3 Example 4 Example 5 Base oil 1 2 3 4 5
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 10 units / reason 6 7 8 1 1
  • Example 11 Example 12 Example 13 Base oil 2 2 2
  • Example 17 Example 18 Example 19 Example 20 Example 20 Example 21 Base oil 1 2 3 4 5
  • Example 22 Example 23 Example 24 Example 24 Example 25 Example 26 Base oil 1 2 3 4 5
  • Example 27 Example 28 Example 29 Example 29 Example 30
  • Example 32 Example 33 Example 34 units; 6 7 8
  • the sample oils of Examples 1 to 44 which are the refrigerating machine oil compositions of the present invention, have kinematic viscosities and refrigerant compatibility when used together with HFC refrigerants. , Electrical insulation, hydrolysis resistance, heat stability and lubricity were all well-balanced and excellent.
  • sample oils of Examples 41 and 2 containing an ester compound having a cyclohexane ring and the sample oils of Examples 43 and 44 containing an ester compound having a cyclohexene ring were thermally and hydrolyzed. Comparison in Stability Test III shows that the former has a small increase in viscosity and the latter has a small increase in total acid value.
  • the refrigerating machine oil composition of the present invention when used in combination with an HFC refrigerant and a natural refrigerant such as carbon dioxide or carbon at a hide port, lubricity, refrigerant compatibility, heat and water It excels in decomposition stability, electrical insulation, etc., and can achieve high efficiency of the refrigeration system.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

Une composition d'huile pour machine de réfrigération contient un composé ester d'acide alicyclique dicarboxylique présentant un cycle alicyclique ainsi que deux groupes ester lesquels sont représentés par la formule générale (1) COOR1 (dans laquelle R1 représente un groupe hydrocarbure C¿1-30? et les R?1¿ de tous les groupes ester peuvent être identiques ou différents), et lesquels sont liés respectivement aux atomes de carbone adjacents mutuellement sur le cycle, formule dans laquelle le composé ester se situe en cis par rapport à la configuration des deux groupes ester.
PCT/JP1999/004496 1999-03-26 1999-08-20 Composition d'huile pour machine de refrigeration WO2000058425A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53030/99A AU5303099A (en) 1999-03-26 1999-08-20 Refrigerating machine oil composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11083867A JP2000273477A (ja) 1999-03-26 1999-03-26 冷凍機油組成物
JP11/83867 1999-03-26

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WO2000058425A1 true WO2000058425A1 (fr) 2000-10-05

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008365A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
WO2002008367A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW482761B (en) * 1999-07-19 2002-04-11 New Japan Chem Co Ltd Dicarboxylic acid diester, a process for preparation thereof and refrigerator lubricating oil containing the diester
JP6773976B2 (ja) * 2017-02-28 2020-10-21 新日本理化株式会社 軸受用潤滑油基油
CN113667522B (zh) * 2021-07-28 2023-01-10 中国石油化工股份有限公司 一种抗微动磨损空调电机轴承低噪音润滑脂及其制备方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH08134481A (ja) * 1994-11-11 1996-05-28 Matsushita Electric Ind Co Ltd 冷凍機作動流体用組成物及びそれを用いた冷凍システム
WO1997021792A1 (fr) * 1995-12-12 1997-06-19 New Japan Chemical Co., Ltd. Huile lubrifiante
JPH09221690A (ja) * 1995-12-12 1997-08-26 New Japan Chem Co Ltd 冷凍機用潤滑油

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134481A (ja) * 1994-11-11 1996-05-28 Matsushita Electric Ind Co Ltd 冷凍機作動流体用組成物及びそれを用いた冷凍システム
WO1997021792A1 (fr) * 1995-12-12 1997-06-19 New Japan Chemical Co., Ltd. Huile lubrifiante
JPH09221690A (ja) * 1995-12-12 1997-08-26 New Japan Chem Co Ltd 冷凍機用潤滑油

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008365A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
WO2002008367A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
US6831045B2 (en) 2000-07-24 2004-12-14 Nippon Oil Corporation Refrigerating machine oil composition
US7045490B2 (en) 2000-07-24 2006-05-16 Nippon Oil Corporation Refrigerating machine oil composition

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JP2000273477A (ja) 2000-10-03

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